Colored photographic direct positive images



United States Patent U.S. CI. 9620 4 Claims ABSTRACT OF THE DISCLOSURE This invention relates to a process for the production of colored photographic direct positive images by means of the simultaneous use of amidrazones which react with the oxidation products of a developer to form stable colorless products, and compounds which under the conditions of the conventional photographic processing either do not react with oxidized developers or only react therewith to form colorless products or products which become colorless during the photographic processing, the said compounds preferably having no developer action and being capable of reacting 'with the developer-modified amidrazone under oxidizing conditions (e.g., in conventional photographic bleaching baths) to form dyes, the processing of the exposed photographic material being carried out under otherwise usual conditions, using a black-and-white or color-forming developer.

The use of organic compounds containing hydrazone groupings the oxidation products of which are colored products are known. By way of example, dihydrazones of a,5-dicarbonyl compounds are described in British patent specification No. 916.657 for the production of direct positive images. These dihydrazones are practically colorless and react at the light-struck areas during the colorforming development with the developer oxidation products to form likewise colorless products. When the silver image is bleached out by means ofan oxiding bath, they are transformed at the unexposed areas into a yellowish orange-colored substance. It is possible in this way to produce colored direct positive images, but these are, however, relatively weak in color. They are suitable for the production of color-correcting masks.

A process for the production of 'colored direct positive images by utilizing the principle described in the aforementioned British patent specification would per se be extremely advantageous. Such a process would be superior to the known color reversal processes, because the method of processing would be substantially simpler, as the second exposure and the second development become superfiuous.

Amidrazones of a specific constitution are used in Belgian Patent 602,250 for the production of colored masking images. The amidrazones are capable of coupling by oxidation with color couplers, so that a colored positive image is formed in the bleaching bath at the unexposed and undeveloped areas remaining after the color development. The principle of the reaction used therein is described in an article by S. Hiinig and F. Miiller, Annalen 651 (1962), pages 73 et seq.

This principle is used in the process described in German Auslegeschrift No. 1,146,751 for the production of colored direct positive images, making use of the difference in the acid, sensitivity between the dyes formed by reaction of common color couplers with the oxidation products of color-forming developers, and the dyes formed by the oxidizing coupling of the amidrazones and color couplers. The process is carried out in such a way that exposure, color development, bleaching and fixing take place in accordance with common-practice whereupon the processed material is treated with a strongly acid aqueous solution to destroy the dyes formed on color de velopment while retaining the dyes formed by the bleaching bath. The great disadvantage of this process is the acid treatment, since the difference in the acid sensitivity of the dyes is not so great that one would be completely and irreversibly destroyed, while the other would be retained in a suitable condition.

It is an object of the present invention to provide a direct positive color photographic process which does not have the aforesaid disadvantages and which permits the production of colored direct positive images of excellent quality in simple manner.

It has now been found that colored direct positive images can be produced, if the usual color couplers in the foregoing color-photographic materials are replaced by compounds which advantageously do not react with developer oxidation products, or at the most only react therewith to form colorless products, which compounds advantageously themselves have no developer effect and which compounds can be reacted with the oxidation products of amidrazones to form colored compounds.

The present invention provides a very simple and inexpensive technique for the production of direct positive color-photographic images which is unexpectedly desirable and which the prior art did not consider possible. Many compounds are suitable for the process of the present invention. Particular utility is exhibited by compounds of the following groups:

(I) Aryl amines, such as phenylamines or naphthylamines or derivatives thereof. The a ryl amines include preferably those of the following formula:

\R/ in which R stands for a phenyl or a naphthyl group, R: and R" which may be like or different, represent hydrogen, alkyl having up to 20 carbpn atoms, aryl preferably phenyl or naphthyl; aralkyl, such as benzyl or phenylethyl or heterocyclic radicals such as pyridine or quinoline.

The substituents R and R" together can stand for the ring members necessary to complete a 5- or 6-membered heterocyclic ring, particularly a saturated ring, such as morpholine, piperidine, pyrrolidine, piperazine and the like. R and/or R", together with the ortho-methine group of the benzene ringv of R, can likewise form 5- or 6-membered heterocyclic rings. Included herein are, for example, rings of the tetrahydroquinoline type. t

The phenyl ring of R in the above general formula can be substituted in any suitable manner, it only being necessary to ensure that either one of the two ortho-positions or the para-position to the' amino group is unsubstituted or substituted with groups, for example sulfo groups which are capable of being split off under the processing conditions.

The following are suitable as substituents: Halogen, such as chlorine or bromine, alkyl or alkoxy radicals containing up to 20 carbon atoms, carboxyl, carboxyl esters, preferably with aliphatic alcohols'containing up to ZO-car bon atoms, sulfo, sulfonamide, or carbonamide radicals, it being possible for the amide groups to be substituted with alkyl radicals containing up to 20 carbon atoms, or acyl radicals, more especially those which are derived from aliphatic carboxylic acids containing up to 20 carbon atoms, and also nitro, nitrile, or amino groups. Substitution in the o-position or m-position is preferred since the p-amino derivatives are less suitable on accountof their often strong'developer action. The amino group can be substituted by alkyl radicals with up to 20 carbon atoms, acyl, more especially an acyl radical which is derived from aliphatic carboxylic acids containing up to 20 carbon atoms, or phenyl. The phenyl ring of R in the above formula can furthermore be substituted by other phenyl or even naphthyl rings in simple manner, or contain these rings in anellated (fused) form.

Since it is obvious that the substituents on the phenyl ring of R in the above formula can in their turn also be substituted, numerous possibilities of variation are provided, it being possible for certain properties such as solubility or the color of the reaction product with the oxidized amidrazones to be modified in the desired manner. In selecting the substituents, it is only necessary to ensure that the resulting products do not impair the photographic properties of the material and, under the usual photographic processing conditions, do not react with developers or the oxidation products thereof or at the most only react therewith to form colorless products. Compounds "with substituents making the molecule resistant to diffusion are preferred.

These compounds can be used in the form of the free amines or as salts of any suitable acids. The following compounds exhibit particular utility:

( NIH-0121325 (II) HMS-( 2) 2 Co n IIIHa OO1BH37 (IV) r m,

C1aHa1 H0 0 0 -NH-o0-OuHm VII H (VIII) CrsHzw CH3 SOQH (XIII) (XIV) HIiI-(CHzM-SOaH -o GE n cum CHioHz smH CHz-C H2011 2 5 no4s- N (X VIII) S 0311 Tertiary amines are particularly suitable for the process according to the invention.

The production of the amines is generally known per se. Thus, the introduction of the radicals providing diffusion resistance into the Compounds I, X, XII and also of the pyrrolidinyl radical into the Compound XI can be performed by reacting the known unsubstituted amines with the corresponding alkyl phenyl halides in a manner which is generally known. Compounds V and XIII are rendered fast to diffusion by acylation reactions. Cornpound III is prepared by reacting the corresponding 1- acetaminophenol, in the form of the alkali phenolate with octadecyl bromide. The free amine is obtained by acid or alkali saponification.

(II) Compounds of the thiazol series, the thiazol ring of which is substituted in 2-position with a sulfosubstituted amino radical. Particularly suitable are 2-sulfonamido-4-phenyl-thiazoles. These compounds preferably include those of the following formula:

R =aryl, preferably a phenyl or naphthyl, which can be substituted with nitro, halogen, such as chlorine or bromine, alkyl preferably alkyl having up to 5 carbon atoms such as methyl or ethyl, hydroxy, alkoxy, having preferably up to 5 carbon atoms, such as methoxy or ethoxy, carboxyl, esterified carboxyl, having preferably up to 5 carbon atoms, amino, alkyl amino, the alkyl group of which having preferably up to 5 carbon atoms, phenyl amino, acylamino with preferably acyl groups, which are derived from aliphatic carboxylic acids, having up to 20 carbon atoms, such as acetyl or stearoyl, or benzyl amino, sulfonamide, sulfo, alkyl sulfon, sulfonyl, or esterified sulfo groups, in particular with aliphatic alcohols having up to 20 carbon atoms;

R hydroxy, alkyl having up to 20 carbon atoms, such as methyl, ethyl, butyl or heptadecyl, olefinically unsaturated alkyl having up to 20 carbon atoms, such as allyl, cycloalkyl, such as cyclohexyl, aryl, preferably phenyl or naphthyl or aralkyl, such as benzyl or phenyl ethyl; the above radicals and preferably the rings of the benzene series can in turn be substituted with hydroxy halogen, such as chlorine or bromine, alkyl preferably alkyl having up to 5 carbon atoms, such as methyl or ethyl, alkoXy, having preferably up to 5 carbon atoms, such as methoxy or ethoxy, carboxyl, esterified carboXyl, having preferably up to 5 carbon atoms, amino, alkyl amino the alkyl group of which preferably has up to 5 carbon atoms,, phenyl amino, acylamino with preferably acyl groups derived from aliphatic carboxylic acids having up to 20 carbon atoms, such as acetyl or stearoyl, or benzyl amino, sulfonamide, sulfo, alkyl sulfon, esterified sulfo groups, in particular With aliphatic alcohols having up to 2 carbon atoms. Particular utility is exhibited by the following compounds:

(XXXVII) OCH;

(XXXVIII) (XXXIX) H C I lL-NlEi-SO The above compounds react with the oxidation products of amidrazones to form brilliant magenta dyes.

The thiazoles are prepared according to common practice. The production of compound XXIX is described in the following:

8.8 g. of 2-amino-4-phenyl-thiazole prepared according to J. Am. Chem. Coc. 46, 2867, are dissolved in 20 ml. of pyridine and mixed with 11.1 g. of 3-nitrobenzene-sulfochloride. A slight spontaneous heating of the reaction mixture occurs. Thereafter the mixture is heated for 15 minutes on a steam bath. The reaction product is precipitated in the form of an oily phase upon adding water. The oily phase is separated and crystallizes after some time. It is recrystallized from acetic acid.

6.6 g. of the compound obtained in step 1 are heated with 3.6 g. R'aney nickel and 20 ml. of methanol. Thereafter it is refluxed and 18 ml. of hydrazine hydrate are added dropwise. After the addition of the hydrazine hydrate is finished, it is refluxed for further 15 minutes and thereafter suction filtered. The filtrate is boiled down, the residue digested with water and suction filtered again. Yield 2.5 g.

g. of a copolymer of maleic acid anhydride-N-vinylpyrrolidone, molar ratio 1:1 (prepared in accordance with German patent specification No. 1,123,913) are dissolved at C. in

30 ml. of dimethylformamide. To this solution are added 2.5 g. of the compound of step 2, and the mixture heated for 3 /2 hours at 100 C. The reaction mixture is cooled and poured into 300 ml. of water. It is suction filtered and the precipitate dried in vacuo at 3040 C. Yield: 4 g. M.P.

above 300 C.

Other thiazole derivatives can be prepared in analogous manner.

Long aliphatic radicals, which render the compounds fast to diffusion (compare Compound XL) are introduced by acylation. Such reactions are known per se.

(III) Compounds of the -imino-A -pyrazoline series. Preferred are pyrazolines of the above type which are fast to diffusion and which are substituted in l-position with a phenylor naphthyl group and which are substituted in 3-position with a substituent containing an aliphatic group having up to carbon atoms, in particular having between 12 and 20 carbon atoms.

Compounds of the above type yield mainly yellow dyes upon reaction with the oxidation products of amidrazones.

These compounds preferably include those of the following formula:

wherein Rg=hydrogen or an organo sulfon grouping having preferably the formula SO -R R =alkyl of up to 20 carbon atoms, aryl such as a phenyl or a naphthyl, or aralkyl, such as benzyl or phenyl ethyl, where the above substituents in particular the phenyl groups can in turn be substituted with nitro, halogen, such as chlorine or bromine, alkyl preferably having up to 5 carbon atoms such as methyl or ethyl, hydroxy, alkoxy having preferably up to 5 carbon atoms such as methoxy or ethoxy, carboxyl, esterified carboxyl having preferably up to 5 carbon atoms, amino, alkyl amino the alkyl group of which has preferably up to 5 carbon atoms, phenyl amino, acylamino with preferably acyl groups, derived from aliphatic carboxylic acids having up to 20 carbon atoms such as acetyl or stearoyl, or benzyl amino, sulfonamide, sulfo, alkyl sulfon, esterified sulfo groups in particular with aliphatic alcohols, having up to 20 carbon atoms;

R =carbamyl, N-alkylcarbamyl the alkyl groups of which have up to 20 carbon atoms, N-phenylcarbamyl, acyl preferably derived from aliphatic carboxyl acids having up to 20 carbon atoms or benzoyl, alkyl having up to 20 carbon atoms such as methyl, ethyl, butyl, heptadecyl, olefinically unsaturated alkyl having up to 20 carbon atoms such as allyl or undecenyl, cycloalkyl such as cyclohexyl, aryl preferably phenyl or naphthyl, or aralkyl such as benzyl or phenyl ethyl; the above substituents particularly the phenyl groups can in turn be substituted with substituents such as nitro, halogen such as chlorine or bromine, alkyl preferably having up to 5 carbon atoms such as methyl or ethyl, hydroxy, alkoxy having preferably up to 5 carbon atoms such as methoxy or ethoxy, carboxyl, esterified carboxyl having preferably up to 5 carbon atoms, amino, alkyl amino the alkyl group of which has preferably up to 5 carbon atoms, phenyl amino, acylamino with preferably acyl groups derived from aliphatic carboxylic acids having up to 20 carbon atoms such as acetyl or stearoyl, or benzyl amino, sulfonamide, sulfo, alkyl sulfon, esterified sulfo groups in particular with aliphatic alcohols having up to 20 carbon atoms;

R =hydrogen, carbamyl, carboxyl, esterified carboxyl groups preferably esterified with aliphatic alcohols having up to 20 carbon atoms, alkyl having up to 20 carbon atoms such as methyl, ethyl, butyl or heptadecyl, olefinically unsaturated alkyl having up to 20 carbon atoms such as allyl or undecenyl, cycloalkyl such as cyclohexyl, aryl preferably phenyl or naphthyl, or aralkyl such as benzyl or phenyl ethyl; the above substituents particularly the phenyl groups can in turn be substituted with substituents such as nitro, halogen such as chlorine or bromine, alkyl preferably having up to 5 carbon atoms such as methyl or ethyl, hydroxy, alkoxy having preferably up to 5 carbon atoms such as methoxy or ethoxy, carboxyl, esterified carboxyl having preferably up to 5 carbon atoms, amino, alkyl amino the alkyl group of which has preferably up to 5 carbon atoms, phenyl amino, acylamino with preferably acyl groups, derived from aliphatic carboxylic acids having up to 20 carbon atoms such as acetyl or stearoyl, or benzyl amino, sulfonamide, sulfo, alkyl sulfon, esterified sulfo groups in particular with aliphatic alcohols having up to 20 carbon atoms.

The phenyl groups of the above substituents can further be substituted by phenyl or naphthyl groups or can contain phenyl or naphthyl groups in anellated form.

Particular utility is exhibited by compounds of the following formulae:

i avn [if (XI J VII) (XL VIII) (XLIX) SOaH SOQH

COOH

The S-imino-M-pyrazolines are prepared according to common practice by reacting acyl acetonitriles with desired hydrazine derivative. Compound XLVIII is, for example, prepared in the following manner:

Other S-imino-M-pyrazolines can be prepared in analogous manner.

(IV) Compounds of the l-phenyl-A -pyrazoline series. Preferred are compounds which contain in 3, 4 or 5-position are attached to the l-phenyl group, an aliphatic su'bstituent having up to 20 carbon atoms preferably between 12 and 20 carbon atoms. This series of compounds react with the oxidation products of amidrazones to form mainly cyan dyes.

These compounds preferably include those of the following formula:

wherein R =represents one of the following substituents:

hydrogen, carbamyl, carboxyl, esterified carboxyl groups preferably esterified with aliphatic alcohols having up to 20 carbon atoms, alkyl having up to 20 carbon atoms such as methyl, ethyl, butyl or heptadecyl, olefinically unsaturatel alkyl having up to 20 carbon atoms such as allyl or undecenyl, cycloalkyl such as cyclohexyl, aryl preferably phenyl or naphthyl, or aralkyl such as benzyl or phenyl ethyl; the above substituents particularly the phenyl groups can in turn be substituted with substituents such as nitro, halogen such as chlorine or bromine, alkyl preferably having up to carbon atoms such as methyl or ethyl, hydroxy, alkoxy having preferably up to 5 carbon atoms such as methoxy or ethoxy, carboxyl, esterified carboxyl having preferably up to 5 carbon atoms, amino, alkyl amino the alkyl group of which has preferably upto 5 carbon atoms, phenyl amino, acylamino with preferably acyl groups derived from aliphatic carboxylic acids having up to 20 carbon atoms such as acetyl or stearoyl, or benzyl amino, sulfonamide, sulfo, alkyl sulfon, esterified sulfo groups in particular with aliphatic alcohols having up to 20 carbon atoms. The phenyl groups of the above substituents can further be substituted by phenyl or naphthyl groups or can contain phenyl or naphthyl groups in anellated form.

Preferred are compounds which are substituted in the 3-position of the pyrazoline ring. The following compounds exhibit particular utility:

N on-G-mrco-mrm -SOaH (LXI) The above compounds are prepared in accordance with known manner by reacting vinylketones such as methylvinylketone, mesityl oxide or chalcone, or p-chloroethyleneketones with phenylhydrazine. The cyclization can be accelerated by heating the reaction mixture, for example, in acetic acid. Compound LVIII is prepared as follows:

63 g. of p-nitrobenzal-acetophenone 33 g. of phenylhydrazine and 300 ml. of acetic acid are refluxed for 1 hour. After cooling the reaction mixture it is poured into water and suction filtered. The precipitate which has a melting point of 113 C. is hydrogenated at 50 C. at a hydrogen pressure of 50 atmospheres in the presence of Raney-nickel in a mixture of methanol and tetrahydrofurane. The solvents are distilled off, the oily residue is treated with methanol, the methanolic solution is separated from the oily residue and the amino compound precipitated from the solution with water. M.P. of the amino compound=1l7 C.

5 g. of a copolymer of vinylpyrrolidone and maleic anhydride are dissolved in 50 ml. of acetic acid at 90 C. To this mixture is added a solution of 5 g. of 1,3-diphenyl- 5(p-aminophenyl)-A -pyrazoline (prepared as above indicated) in 25 ml. of dimethylformamide and the mixture heated for 20 minutes to a temperature of 90 C. Thereafter, the reaction mixture is poured into methanol and suction filtered. The precipitate formed is washed with methanol and dried, 7 g. of Compound LVIII is obtained.

Other l-phenyl-A -pyrazolines can be prepared in analogous manner, for example, as described in:

M. Maire, Bull. Soc. Chim. France (4) 3, 272- (1908), K. V. Auwers, A. Kreuder, Ber. Disc. Chem. Ies. 58, 1974-86 (1925). US. Patent No. 2,976,295.

Amidrazones are compounds which contain the group mg v 16 No. 602,250 and German Auslegeschrift 1,146,751. Such compounds include those of the following formula:

Y represents a direct chemical bond, a vinylene group, an azomethine group or a phenylene group; X represents alkyl preferably of up to 18 carbon atoms such as methyl, ethyl, butyl, hexyl, palmityl or heptadecyl, olefinir cally unsaturated alkyl having up to 18 carbon atoms such as allyl; aryl such as a phenyl or a naphthyl; aralkyl such as benzyl or phenylethyl; or cycloalkyl such as cyclopentyl or cyclohexyl. The above groups, particularly the phenyl radicals, may in their turn be substituted, for example, with halogen such as chlorine or bromine; alkyl such as methyl or ethyl with advantageously up to 5 carbon atoms; hydroxy; alkoxy preferably having up to 5 carbon atoms such as methoxy or ethoxy, carboxyl, carboxy ester preferably'with aliphatic alcohols having up to 18 carbon atoms, amino, acylamino preferably with acyl groups from aliphatic carboxylic acids having up to 20 carbon atoms such as acetylamino or stearoylamino, alkylamino having preferably up to 18 carbon atoms, sulfo, aminosulfonyl, esterified sulfo groups or alkylsulfonyl having up to 18 carbon atoms;

R; can represent hydrogen; alkyl with up to 20v carbon atoms such as methyl, ethyl, butyl or heptadecyl; olefinically unsaturated alkyl having preferably up to 18 carbon atoms such as allyl; cycloalkyl, such as cyclopentyl or cyclohexyl; aryl advantageously phenyl or naphthyl; or aralkyl such as benzyl or phenylethyl. It is possible for the above groups in particular the phenyl radicals, to be substituted in their turn, for example, with halogen such as chlorine or bromine; alkyl such as methyl or ethyl With advantageously up to 5 carbon atoms; hydroxy, alkoxy preferably having up to 5 carbon atoms such as methoxy or ethoxy, carboxyl, carboxy ester preferably with aliphatic alcohols having up to 18 carbon atoms, amino, acyl'amino preferably with acyl groups from aliphatic carboxylic acids having up to 20 carbon atoms such as acetylamino or stearoylamino, alkylamino having preferably up to 18 carbon atoms, sulfo, aminosulfonyl, esterified sulfo groups or alkylsulfonyl having up to 18 carbon atoms;

R can represent hydrogen; alkyl with up to 20 carbon atoms such as methyl, ethyl, butyl, stearyl or heptadecyl; olefinically unsaturated *alkyl of preferably up to 18 carbon atoms such as allyl; cycloalkyl such as cyclopentyl or cyclohexyl; aryl preferably phenyl or naphthyl; or aralkyl such as benzyl or phenylethyl. It is possible for the above groups, advantageously the phenyl radicals, to be substituted in their turn, for example was halogen such as chlorine or bromine; alkyl such as methyl or ethyl with advantageously up to Scarbon atoms; hydroxy; alkoxy preferably having up to5 car bon atoms such as methoxy or ethoxy, carboxyl, carboxy ester preferably with aliphatic alcohols having up to 18 carbon atoms, amino, acylamino preferably with acyl groups from aliphatic carboxylic acids having up to 20 carbon atoms such as acetylamino or stearoylamino, alkylamino having preferably up to 18 carbon atoms, sulfo, aminosulfonyl, esterified sulfo groups or alkylsulfonyl having up to 18 carbon atoms; preferred substituents are those which have a diffusion-resistant or water-solubilizing action;

X and R and/ or X and R together can moreover repre sent the methylene or methine groups or hetero atoms such as O, S, Se or N, necessary for completing a 5- membered or 6-membered heterocyclic ring which may contain an anellated benzene ring; the combination X H, and R can, for example, form the following heterocyclic rings: oxazole, benzoxazole, thiazole, benzthiazole, selenazole, benzselenazole, imidazole, benzimida- I zole, pyrrolidone, quinoline, piperidine or pyrimidine; 5 -N the combination X and R can represent piperidine, morpholine, pyrazole, pyrazoline, pyrrolidine or oxazolidine; 0

R represents hydrogen, acyl preferably acyl groups from aliphatic carboxylic acids having up to 20 carbon atoms 10 C=NNHSOr(C I)1u Ha such as acetyl, stearoyl or palmitoyl, or a carbonamide N group which can be substituted with alkyl with prefer- I ably up to 18 carbon atoms, or aryl preferably phenyl or naphthyl; (7)

R represents hydrogen, a sulfo group, aminosulfonyl,

alkylsulfonyl with preferably up to 20 carbon atoms such as methylsulfonyl, ethylsulfonyl or stearylsul- N fonyl, arylsulfonyl, preferably phenylsulfonyl or naph- I thylsulfonyl, aminosulfonyl substituted with alkyl or phenyl having up to 20 carbon atoms, or a sulfonyl 20 (8) 3 group which is bonded to a heterocyclic system, or carn c c=NNHsO1(0H1)1tCH| bonamide; the above groups, in particular the phenyl radicals, may in their turn be substituted, for example with halogen such as chlorine or bromine; alkyl such (9) as methyl or ethyl with advantageously up to 5 carbon /N atoms; hydroxy; alkoxy preferably having up to 5 car- NNH$OI-(CH91PCH8 bon atoms such as methoxy or ethoxy, carboxyl, carboxy ester preferably with aliphatic alcohols having up to 18 carbon atoms, amino, acylamino preferably with (m) acyl groups from aliphatic carboxylic acids having up to 20 carbon atoms such as acetylamino or stearoylamino, alkylamino having preferably up to 18 carbon l atoms, sulfo, aminosulfonyl, esterified sulfo groups or alkylsulfonyl having up to 18 carbon atoms; preferred OH! in this connection are substituents which have a diffusion-resisting action; (11) S OH; R and R together can represent the acyl radical of an aliphatic saturated or unsaturated 1,2- or 1,3-dicarboxylic acid or an aromatic o-dicarboxylic acid, in particular an o-dicarboxylic acid of benzene, so that the compound containing them has a S-membered or 6- 12 membered heterocychc ring, for example, the malerc imide ring, the succinimide ring, glutarimide ring or phthalimide ring. N Suitable compounds include the following: S

I CH1 wherein 11:4, 5 or 6 HaCN-CH:

n-Nn-sol-(cnou-om LfqLN-NH-SOr- (0 2) "-0 Ha Preparation of the amidrazones Processes for the production of the foregoing compounds are generally known and particularly described in the Belgian patent referred to. Some specific examples for the production of some of the compounds listed above are given in the following:

Compound 1 20 g. of N-ethyl benzthiazolone hydrazone,

35 g. of octadecyl sulphonyl chloride, and

8 g. of pyridine are boiled under reflux for 2 hours in 600 cc. of acetonitrile. On cooling,

39 g. (69.1% of the theoretical yield) of 3-ethyl-2-benzthiazolone-fl-n-octadecyl sulfonyl hydrazone of melting point 111 to 114 C. crystallizes out.

Compound 2 15 g. of a vinyl pyrrolidone-maleic anhydride copolymer as described in British patent specification No. 954,924 are dissolved at 90 to 100 C. in

100 cc. of glacial acetic acid.

In this solution there are introduced 20 g. of 3-amino phenyl sulfonyl hydrazone of N-ethyl- 2-benzthiazolone, dissolved in 200 cc. of dimethylformamide. The mixture is kept for 1 hour at 100 C. and poured into 4 liters of water suction-filtered and dried in vacuo at room temperature. Yield: 30 g.

Compounds 3 and 4 can be prepared in an analogous manner.

(1)4-amino-N,N-diethyl aniline sulfate g 2.5 Anhydrous sodium sulfite g 2.5 Potassium bromide g 1.0 Potassium carbonate g 75.0 Water "liter-.. 1

In the above composition the 4-amino-N,N-diethyl aniline sulfate can be replaced by:

G. (2)4-amino-N,N-butyl butane sulfoaniline 5.0 (3)4-aminophenol 5.0 (4)p-Methylamino phenol 5.0 (5)-Glycine 15 (6)1-phenyl-3-pyrazolidone 3 (7)4-amino phenimine 5 (8)Hydroquinone 5 (9)Pyrocatechol 5 (B) Bleaching bath-In principle, it is possible to employ the conventional bleaching baths or combined bleaching and fixing baths, for example, aqueous solutions of complexes of trivalent iron or trivalent cobalt with aminopolycarboxylic acids such as ethylene diamine tetraacetic acid, nitrilo triacetic acid or the like as described, for example, in German patent specification No. 866,605, or aqueous solutions of potassium bichromate, or potassium ferricyanide. Suitable baths are, for instance, a 20% by weight solution of potassium ferricyanide or a 10% by weight aqueous solution of potassium bichromate. The required pH can be adjusted by adding the necessary amount of aqueous solution of acids or alkali metal hydroxides or carbonates.

(C) Fixing bath.Any desired photographic fixing baths can be used. The fixing agent, however, must not have reducing properties. Preferred are aqueous solutions of salts of .thiosulfate, e.g., sodium thiosulfate, potassium thiosulfate or ammonium thiosulfate. The fixing agents can be used as about 20% by Weight aqueous solutions.

Other conventional photographic processing baths can also 'be employed. In principle, they are, of course, not essential to the process, but they are often advantageous. They include, for example, stop baths which have a pH down to 3, or hardening baths.

It might be advantageous in certain cases to rinse the photographic material between the different processing steps. After the final rinsing, drying can be performed by means of conventional dryers for photographic materials at slightly raised temperatures.

The silver halide emulsions are produced in accordance with common practice. The preparation involves three separate steps: 1) precipitation of the silver halide and physical ripening in the presence of gelatin, (2) freeing the resulting emulsion of excess water-soluble salt usually by washing and (3) after-ripening or chemical ripening to obtain the desired speed or sensitivity.

The amidrazones or the reaction components which react with the oxidation products of amidrazones can be added at any desired stage to the light-sensitive silver halide emulsion layer. Under the term reactants are understood in the following both the amidr-azones and compounds which react with the oxidation products of amidrazones to form a dye. In the preparation of the photographic emulsions of the present invention the arnidrazones are advantageously incorporated in the finished emulsion after the chemical ripening. It is convenient to add the reactants of the present invention from solutions in appropriate solvents. The solvent should, of course, be completely free from any deleterious eifect on the silver halide emulsion. Water or lower aliphatic alcohols or admixtures thereof have proven satisfactory as solvents for the majority of the :amidrazones of the invention.

According to another method, the reactants are first dissolved in an oily organic material, and this combination is dispersed in a finely divided state throughout the emulsion. The concentration of the amidrazones in the emulsion can vary widely from about 1-120 preferably 2-50 g. per mol of silver halide, their specific concentration varying according to the type of light-sensitive emulsion and according to the effects desired. Preferred are concentrations of between 5 and 20 g. per mol of silver halide. The most suitable concentration for any given emulsion will be apparent upon making the test customarily used in the art.

The compounds which react with the oxidation products of amidrazones are added in amounts of 1'120 g. preferably 15-70 g. per mol of silver halide.

As silver halides for the light-sensitive emulsions, it is possible to employ silver chloride or silver bromide, possibly with a few mol percent of silver iodide, or mixtures of these halides.

The usual hydnophilic colloids are suitable as binders, such as, advantageously, gelatin, although this can be wholly or partially replaced by other film-forming materials, such as carboxymethyl cellulose, polyvinyl alcohol, alginic acid or derivatives thereof such as salts, esters or amides, polyvinyl pyrrolidone and the like.

The emulsions of the present invention can be chemically sensitized by any of the accepted procedures. The emulsions can be treated with salts of the noble metals such as ruthenium, rhodium, palladium, iridium and platinum. Suitable compounds are Well known in the art. The emulsions can also be sensitized with gold salts as described by R. Koslowsky Z.wiss.phot. 46, 65-72 (1951). V The emulsons can also be chemically sensitized with reducing agents such as stannous salts, polyamines, sulfur compounds, such as described in the U8. Patent No. 1,574,944, polyethylene oxides and the like.

The emulsions can also be optically sensitized with the ordinary sensitizing dyes, cyanines or merocyanines. The emulsions can be stabilized with any of the known stabi- 23 lizers such as mercury compounds, triazoles, azaindenes, such as disclosed by Birr in Z.wiss.phot., vol. 47 (1952) pages 2-28.

The emulsions may be hardened by any suitable hardener, such as formaldehyde and halogen substituted aliphatic acids such as mucobromic acid.

The process according to the present invention is suitable for the production of mono-color and also multicolor direct positive images. The process can further be applied for the production of masking images for the color-correction of conventional multicolor images. In the case of so-called built-in masks, the multicolor images can be produced in conventional manner.

For the production of multicolor direct positive photographic images, photographic multi-layer materials are used which contain in the usual manner light-sensitive layers which are sensitive to the three primary colors of the visible spectrum. The multicolor images preferablyconsist of the subtractive colors yellow, cyan and magenta.

EXAMPLE '1 A silver bromide emulsion containing, per 100 ml., 1.0 g. of amine I and 1.0 g. of amidrazone 2 is applied to a suitable support, exposed to light and developed for minutes at 20 C. in the following developer:

4-amino-N-butyl-N-w-sulfobutyl anilin g 5.0 Anhydrous sodium sulfite g 1.0 Potassium bromide g-.. 1.0 Potassium carbonate ..g 75.0 Water liter 1 Bleaching and fixing is thereafter performed in accordance with common practice employing baths of the type described above. A positive violet image is obtained.

If amine I in the above material is replaced by the same amount of other aromatic amines according to the invention, images of the following color are obtained:

If the above photographic material described in Example 1 but which contains 1 g. of amine II is processed in a black and White developer of the methylamino phenol type, e.g., the developer A4 a blue positive image is likewise obtained.

EXAMPLE 3 In corresponding manner, a blue positive image is obtained if the photographic material of Example 1 is processed with an amino phenol developer, for example, the developer A3, a blue direct positive image is obtained.

EXAMPLE 4 A silver bromide emulsion containing, per 100 ml., 1 g. of Compound XXIX and 1.0 g. of amidrazone 2 is applied to a suitable support, exposed to light and developed for 5 minutes at 20 C. in the following developer:

4-amino-N-butyl-N-w-sulfobutyl-anilin g 5 Anhydrous sodium sulfite g 1. Potassium bromide g 1 Potassium carbonate g 5 Water Bleaching and fixing is thereafter performed in accordance with common practice employing baths of the type described above. A positive magenta image is obtained.

If Compound XXIX in the above material is replaced by the same amount of another compound of the thiazol series according to the invention, images of the following color are obtained:

liter Table 2 Compounds of the thiazol series: Image color XXX Magenta XXXI Magenta XXXII Red XXXIX Red EXAMPLE 5 If the photographic material described in Example 4 and which contains 1 g. of Compound XXXI is processed in a black-and-white developer of the methyl amino phenol type, e.g., the developer A4, a magenta image is obtained.

In corresponding manner a magenta image is also obtained if the photographic material is developed with an amino phenol developer, for example, the developer A3.

EXAMPLE 6 EXAMPLE 7 A silver bromide emulsion containing, per ml. 1.0 g. of Compound XLI and 1.0 g. of amidrazone 2 is applied to a suitable support, exposed to light and developed for 5 minutes at 20 C. in the following developer:

4-amino-N-butyl-N-w-sulfobutylanilin g. 5. 0 Anhydrous sodium sulfite g 1. 0 Potassium bromide g 1. 0 Potassium carbonate g 75.0 Water liter 1 Bleaching and fixing is thereafter performed in accordance with common practice employing baths of the type described above. A positive yellow image is obtained.

If Compound XLI in the above material is replaced by the same amount of Compounds XLII to LVII direct positive yellow images are likewise obtained.

EXAMPLE 8 A silver bromide emulsion containing per 100 ml. 1.0 g. of Compound LVIII and 1.0 g. of amidrazone 2 is applied to a suitable support, exposed to light and developed for 5 minutes at 20 C. in the following developer:

4-amino-N-butyl-N-w-sulfobutylanilin g S. 0 Anhydrous sodium sulfite g-.. 1. 0 Potassium bromide g 1. 0 Potassium carbonate g 75. 0 Water liter 1 Bleaching and fixing is thereafter performed in accord- 25 ance with common practice employing baths of the type described above. A positive cyan image is obtained.

If the Compound LVIII in the above material is replaced by the same amount of Compounds LIX t LXVI, direct positive cyan images are likewise obtained.

We claim:

1. In the process for producing a direct positive dye image in a photographic layer containing an amidrazone compound that reacts with the oxidation products of a photographic developer during development without forming color but forms color during the bleaching step of photographic processing by reaction with a color coupler under the oxidizing conditions of the bleaching, the improvement according to which the color coupler is replaced by a different colorless compound which is an aryl amine, a thiazole, a S-amino-M-pyrazoline or a l-phenyln -pyrazoline that will not give rise to color during color development but will produce color by reaction with the amidrazone compound during the bleaching.

2. In a photographic material having a silver halide emulsion layer containing a color coupler and an amidrazone compound that reacts with the oxidation products of a photographic developer during development without forming color but forms color during the bleaching step of photographic processing by reaction with the color coupler under the oxidizing conditions of the bleaching, the improvement according to which the color coupler is replaced by a difierent colorless compound which is an aryl amine, a thiazole, a S-amino-M-pyrazoline or a l-phenyl-A -pyrazoline that will not give rise to color during color development but will produce color by reaction with the amidrazone compound during the bleaching.

3. The combination of claim 1 wherein the compound that replaces the color coupler is selected from those having the following formulae:

wherein R stands for phenyl or a naphthyl;

R and R separately represent hydrogen, alkyl having up to 20 carbon atoms, aryl, aralkyl or heterocyclic radicals;

R and R together represent the ring members necessary to complete with the N a 5- or 6-membered heterocyclic ring; or

R' together with the o-carbon atom of the benzene 26' ring of R, represent the ring members necessary to complete with the N a 5- or 6-membered heterocyclic ring; or

R" together with the o-carbon atom of the benzene ring of R represent the ring members necessary to complete with the N a 5- or 6-membered heterocyclic ring;

R represents an aryl group;

R stands for hydroxyl, alkyl of up to 20 carbon atoms,

olefinically unsaturated alkyl having up to 20 carbon atoms, cycloalkyl, aryl or aralkyl;

R represents hydrogen or an organo sulfon grouping;

R stands for carbamyl, N-alkyl carbamyl, N-phenyl carbamyl, acyl, alkyl having up to 20 carbon atoms, olefinically unsaturated alkyl having up to 20 carbon atoms, cycloalkyl, aryl or aralkyl; and

R and R separately represent hydrogen, carbamyl, carboxyl, esterified carboxyl, alkyl having up to 20 carbon atoms, olefinically unsaturated alkyl having up to 20 carbon atoms, cycloalkyl, aryl or aralkyl.

4. The combination of claim 2, wherein the compound that takes the place of the color coupler is selected from those having the following formulae:

wherein R stands for a phenyl or a naphthyl;

R and R" separately represent hydrogen, alkyl having up to 20 carbon atoms, aryl, aralkyl or heterocyclic radicals; or

R and R" together represent the ring members necessary to complete with the N a 5- or 6-membered heterocyclic ring; or

R together with the o-carbon atom of the benzene ring of R, represent the ring members necessary to complete with the N a 5- or 6-membered heterocyclic ring; or

R together with the o-carbon atom of the benzene ring of .R represent the ring members necessary to complete with the N a 5- or 6-membered heterocyclic ring;

R represents an aryl group;

R stands for hydroxyl, alkyl of up to 20 carbon atoms, olefinically unsaturated alkyl having up to 20 carbon atoms, cycloalkyl, aryl or aralkyl;

3,443,942 27 28 R represents hydrogen or an organo sulfon grouping; References Cited R stands for carbamyl, N-alkyl carbamyl, N-phenyl UNITED STATES PATENTS esterified carboxyl, alkyl having u to 20 carbon carbamyl, acyl, alkyl having up to 20 carbon atoms, 3,293,032 12/1966 Jaeken at 96 53 olefinically unsaturated alkyl having up to 20 carbon atoms cycloalkyl, aryl or aralkyl; and 5 NORMAN G. TORCHIN, Pumary Exammer.

R and RF, separately represent hydrogen, carboxyl, A. T. SUROPICA, Assistant Examiner. esterified carboxyl, alkyl having up to 20 carbon atoms, olefinically unsaturated alkyl having up to 20 US. Cl. X.R. carbon atoms, cycloalkyl, aryl or aralkyl. 10 969, 21

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3 443 942 Dated May 1969 Inventor) Walter Puschel et a1,

It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Column 14 line 69 "Ber.Disc.Chem.Jes should read Ber.dtsch.chem.Ges Column 19 formula 20 that portion of the formula reading "-CH should read -CH Column 15 formula LXVI that portion of the formula reading CH N should read CH If Signed and sealed this 22nd day of December 1970.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. WILLIAM E. SCHUYLER, JR. Attesting Officer Commissioner of Patents FORM PO-105O (10-69) USOMM DC 50376 p69 n as covnlmnn nmmuc orncz: nu c-au-su 

